Monohaloalkyl and polyhaloalkyl lactams



United States Patent 3,404,147 MONOHALOALKYL AND POLYHALOALKYL LACTAMSRaymond L. Mayhew, Summit, and Frederick Grosser, Midland Park, N.J.,assignors to GAF Corporation, a corporation of Delaware N0 Drawing.Continuation-impart of application Ser. No. 340,799, Jan. 28, 1964. Thisapplication Dec. 22, 1965, Ser. No. 515,728

9 Claims. (Cl. 260239.3)

ABSTRACT OF THE DISCLOSURE 6- and 7-membered lactams arepolyhaloalkylated by heating a mixture consisting of from 5 to moles ofsaid lactams with one mole of a monohaloor POlYllIilO-aolefin of atleast 2 carbon atoms in the presence of approximately from 0.05 to 0.25mole of an organic peroxide at a temperature of from 80 to 200 C.

This application is a continuation-in-part of our application Ser. No.340,799, filed on Jan. 28, 1964, now abandoned.

This invention relates to a new and useful class of monohaloalkyl andpolyhaloalkyl lactams and to the process of preparing the same.

To provide a new and useful class of monohaloalkylated andpolyhaloalkylated 5-, 6- and 7 membered lactams and the process ofpreparing the same constitutes the principal object of the presentinvention.

Other objects and advantages Will become manifest from the followingdescription.

The foregoing objects are attained by the addition of a monohaloorpolyhalo-a-olefin of at least 2 carbon atoms to a 5-, 6- or 7-memberedlactam while employing an organic peroxide as the initiator. Theaddition (monoor poly-haloalkylation) is readily accomplished by heatinga mixture consisting of from 5 to 20 moles of a 5-, 6- or 7- memberedlactam with one mole of a monohaloor polyhalo-u-olefin of at least 2carbon atoms, in the presence of approximately from 0.05 to 0.25 mole ofan organic peroxide, under pressure in a stainless steel rocker bomb ata temperature of 80200 C. for a period of time ranging from 5 to 24hours. The lactam, monohaloor polyhalo-a-olefin, if not gaseous, and theorganic peroxide, are added into the stainless steel rocker bomb. Themonohaloor polyhalo-a-olefin, if gaseous, is injected to the bombthrough its gas valve after the addition of the lactam and organicperoxide. The bomb is then sealed, heated and maintained with shaking atthe said temperature and period of time. The pressure developed in thebomb may range from 50 to 1000 p.s.i.g. After cooling the contents ofthe bomb to room temperature, they are discharged into any suitablevacuum distillation equipment to remove the excess lactam and theresidual product, monohaloalkylor polyhaloalkyl-lactam, recovered eitheras a liquid or solid of a boiling point higher than that of the startinglactam.

The 5-, 6- and 7-membered lactams that are reacted with a monohaloorpolyhalo-u-olefin of at least 2 carbon atoms in accordance with thepresent invention are characterized by the following formula:

wherein R and R represent either hydrogen, methyl or ethyl group, Rrepresents either hydrogen, alkyl of from 1 to 18 carbon atoms, aminoalkyl of from t to 18 carbon 3,404,147 Patented Oct. 1, 1968 atoms,hydroxy alkyl of from 2 to 18 carbon atoms and n represents an integerof from 1 to 3 so as to complete a 5-, 6- or 7-membered heterocyclicring system.

As examples of such lactams, the following are illustrative:2-pyrrolidone, S-methyl-Z-pyrrolidone, 5,5-dimethyl-Z-pyrrolidone,S-ethyl-Z-pyrrolidone, S-methyl-S- ethyl-Z-pyrrolidone, Z-piperidone,6-methyl-2-piperidone, 6-ethyl-2-piperidone, 6,6-diethyl-2-piperidone,caprolactam, 7-methyl caprolactam, 7-ethyl caprolactarn, 7,7-diethylcaprolactam.

The N-substituted lactams, wherein the substituent is characterized by Rin the foregoing formula, are readily prepared by reacting thecorresponding lactones with alkyl primary amines of from 1 to 18 carbonatoms, alkyl diamines of from 2 to 18 carbon atoms and alkanol amines offrom 2 to 18 carbon atoms by the well-known and established conventionalprocedures.

As examples of alkyl primary amines which may be reacted with thecorresponding lactones to arrive at an N-alltyl substituent of from 1 to18 carbon atoms, the following are illustrative: methyl amine, ethylamine, n-propyl amine, n-butyl amine, n-hexyl amine, n-octyl amine,decyl amine, lauryl amine, dodecyl amine, hexadecyl amine, octadecylamine.

As examples of alkyl diamines which may be reacted with thecorresponding lactones to yield amino N-substituted amino alkyl of from2 to 10 carbon atoms as characterized by R in the above formula, thefollowing are illustrative: ethylene diamine, trimethylene diamine,tetramethylene diamine, hexamethylene diamine, octamethylene diamine,decamethylene diamine, octadecamethylene diamine.

As examples of alkanol amines which are reacted with the correspondinglactones to yield N-hydroxy alkyls of from 2 to 18 carbon atoms, ascharacterized by R in the foregoing formula, the following areillustrative: ethanol amine, propanol amine, butanol amine, hexanolamine, octanol amine, decanol amine, dodecanol amine, hexadecanol amine,octadecanol amine.

Any monohaloor polyhalo-a-olefin of at least 2 carbon atoms may beemployed in the reaction of the foregoing lactams, the only restrictionbeing that such olefin contain an ethylenic unsaturation in tat-positionand that the number of carbon atoms therein be at least 2 to as manycarbon atoms as are available or can be made available in such olefinsby synthesis. In other Words, the length of the carbon chain in suchmonohaloand polyhalo-aolefins is immaterial since they will all reactwith the lactams under the foregoing reaction conditions.

As examples of monohaloand polyhalo-a-olefins, which react with theforegoing lactams, the following are illustrative:

dichlorovinylidene fluoride (CCl,=CF chlorovinylidene fluoride (CHCI=CFchlorotrifluoroethylene (CCIF CF tetrofluoroethylene (CF CFtetrachloroethylene (CCIFCCl vinylidene fluoride (CH CF vinylidenechloride (CH CCI vinylidene chlorofiuoride (CHFCClF) s-dichloroethylene(CHCI CHCI) l,Z-dichloro-1,2-difluoroethylene (CCIF CCIF)1,2-difluoroethylene (CHF CHF) 1-chloro-2-fluoroethylene (CHF CHCI)1-dichloro-Z-iluoroethylene (CHF CCI trichloroethylene (CHCl=CCltrifiuoroethylene (CF-FCHF) 1-dichloro-2-difiuoroethylene (CFFCClchlorotrifiuoroethylene (CFFCCIF) 1-chloro-2-difiuoroethylene (CF CHCI)1-dichloro-Z-difluoroethylene (CF CCI 3 fluorotrichloroethylene (CCICCIF) vinyl chloride (CH CHCl) vinyl fluoride (CH CHF) allyl chloride(CH =CH-CH Cl) B,'y-dichloro-1-propylene (CH -CclcH Cl)4-chloro-l-butene (CH CH-CH,CH Cl) 3 ,4-dichlorol-butene (CH CHCHClCHCl)3,3,4,4,4-pentafiuoro-l-butene (CH CH-CF CF 5-chloro-l-pentene (CH==CH-CH CH CH Cl) 3,3,4,4,5,5,S-heptafiuoro-l-pentene3,3,4,4,5,5,6,6,6-nonafluoro-l-hexene As organic peroxide catalysts(initiators) for the monohaloalkylation and polyhaloalkylation of theforegoing lactams, any one of the known tertiary-alkyl organic peroxidesand hydroperoxides such as, for example, di-tbutyl peroxide, t-butylperbenzoate, di-ti-butyl perphthalate, t-butyl-pentamethyl-ethylperoxide, t-butyl-triphenylmethyl peroxide, di-t-amyl peroxide,bis-(triethylmethyl) peroxide, bis (triphenylmethyl)peroxide, 2,5dimethylhexyl-2,5 dihydroperoxide, 2,5 dimethyl-2,5 di(t-butylperoxy)hexane, 2,5 dimethylhexyl 2,5 di(peroxy benzoate), t-butylhydroperoxide, para-methane hydroperoxide, t-butyl peroctotate and thelike may be used.

The positions at which mono-haloalkylation, di-haloalkylation andtri-haloalkylation occurs in the lactam ring varies and is dependent onthe nature of the lactam. For example, when the lactam is free fromlower alkyl substituents in the omega position to the carbonyl and on ithe nitrogen atom, i.e., wherein R, R and R in the foregoing formula arehydrogen, and the mole ratio of such lactam to monohaloorpolyhalo-a-olefin is 5 to 20, monosubstitution by a haloalkyl takesplace at the alpha and omega positions to the carbonyl in the lactamring. In other words, a mixture of two monosubstituted isomers isobtained.

With lactams wherein R and R in the foregoing formula are lower alkyland R is hydrogen, monosubstitution by a haloalkyl takes place ina-position to the carbonyl. However, with lactams wherein R or R arelower alkyl and R is either alkyl, aminoalkyl or hydroxyalkyl, isomericmonosubstitution by a haloalkyl takes place in a-position to thecarbonyl and on the first carbon of the R group immediately adjacent tothe nitrogen atom of the lactam ring. The latter isomeric distributioncan be exemplified with a haloalkylated N-substituted-S- methylpyrrolidone by the following illustration:

wherein R is either hydrogen, alkyl, aminoalkyl or hydroxyalkyl of from1 to 17 carbon atoms.

With a ratio of less than 5 moles of lactam (wherein R, R, and R in theforegoing formula are hydrogen) per mole of monohaloorpolyhalo-a-olefin, substantial disubstitution, i.e., 2:1 adducts, takesplace in the aand omega (w) positions of the lactam ring as well aspropagation where one or more additional moles of monohaloorpolyhalo-a-olefin add to the first mole which had added to the lactamring. This propagation is termed polyalkylation as distinguished frommono-, diand trihaloalkylation. In other words, the tendency towardsdiand poly-substitution at the active sites of the lactam ring increasesas the ratio of lactam to the monohaloor polyhalo-u-olefin decreasesbelow 5 moles of lactam per mole of said olefin.

The distribution of the isomeric products obtained in accordance withthe present invention was shown by complete separation of the isomers bypreparative vapor phase chromatography (VPC), elemental analysis,infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy.

The pure isomer is readily separated from the reaction mixture by gaschromatograph separation using a preparation column. The productscontaining from I to 3 isomeric haloalkyl groups, may be, if desired,separated by fractional distillation. However, for the applications forwhich these haloalkylated lactams are intended, products consisting ofmixed isomeric haloalkyl lactam can be used per se, and in someinstances are preferred over anyone of the pure isomers.

The haloalkylated lactams prepared in accordance with the presentinvention are new compounds having new and useful applications as willbe noted hereinafter. The new compounds are characterized by thefollowing formulae:

wherein R, R R and n have the same values as above and the X5 areindependently selected from the group consisting of hydrogen,monohaloalkyl and polyhaloalkyl of at least 2 carbon atoms, and whereinat least one of the X5 is selected from said monohaloalkyl andpolyhaloalkyl groups.

Instead of employing any one of the foregoing individual monohaloorpolyhalo-u-olefins, a mixture of two or mor of such olefins may beemployed as the haloalkylating medium to yield mixed haloalkylatedlactams.

The following examples will show how a mono-, haloand polyhalo-e-olefinare employed to haloalkylate a lactam and characteristics of theresulting product.

EXAMPLE 1 Into a one-liter stainless steel shaker bomb, after a nitrogenpurge, there were charged the following reactants:

Since the allyl chloride is a liquid at room temperature, it was addeddirectly with the other components. The bomb was then sealed, heatedwith shaking and maintained at 130-140 C. for 10 hours. The contentsafter cooling and venting the bomb were transferred into a one-literreaction flask and the excess reactants removed in vacuum. The residuewas then carefully distilled in vacuum using a 250-ml. distillationflask and a 10" long glass helix packed column. The liquid product wascollcclcd at a range of 110 C. and 0.5-1.0 mm. Hg. It weighed 17.5grams, corresponding to a total of 12% yield based on the allylchloride. The product thus obtained was fractionated by vapor phasechromatography (VPC) using a preparative column. The two fractions thatwere obtained were analyzed and their structure determined by elementalanalysis, infrared (IR) and by nuclear magnetic resonance (NMR)spectroscopy as follows:

(l 5-(3-chloropropyl)pyrrolidone.

(2) 3-(3-chloropropyl)pyrrolidone.

The isometric distribution of these two fractions was found to be in theratio of 2:1. In other words, isomer No. l was twice as much as isomerNo. 2.

EXAMPLE 2 Example 1 was repeated with the exception that the allylchloride was replaced by 123 grams (0.5 mole) of3,3,4,4,5,5,6,6,6nonafluoro-l-hexene. The product obtained weighed 86grams corresponding to a total of 52% yield based on the polyfluoroolefin. After fractionation of the product on a preparative VPC column,two fractions were obtained.

Elemental analysis, IR and NMR studies showed the EXAMPLE 3 Example 1was again repeated with the exception that 765 grams of Z-pyrrolidonewere replaced by 594 grams (6 moles) of N-methyl-Z-pyrrolidone and the69 grams of allyl chloride were replaced by 90 grams (0.6 mole) ofhexafluoropropylene. The liquid product was collected at a range of 95-ll0 C. and 1-6 mm. Hg. It weighed 107 grams corresponding to a 72%yield based on the hexafluoropropylene. After fractionation of theproduct on a preparative VPC column, three fractions were obtained.

Elemental analysis, IR and NMR studies showed the following structuresof the three fractions:

(1) 5-(3,3,3,2,1,1-hexafluoropropyl) N methyl 2- pyrrolidone.

(2) 3-(3,3,3,2,l,l hexafluoropropyl) N methyl-2- pyrrolidone.

(3) N (4,4,4,3,2,2 hexafluoro 1-butyl)-2-pyrrolidone.

The three isomeric products are liquids at room temperature. The ratioof isomers (1), (2) and (3) are 60:25:15, respectively.

EXAMPLE 4 Into a one-liter stainless steel shaker bomb, after a nitrogenpurge, was charged a solution of the following reactants:

2-piperidone=600 grams (6.0 moles),

2,5 dimethyl-2,5-di(t-butylperoxy)hexene (95%)=l5.0

grams (0.049 mole),

3.3,4,4,5.5,5-heptafluoro-1-pentene=98 grams (0.5 mole).

The bomb was then immediately sealed, heated with shaking and maintainedat 140-160 C. for 16 hours. After cooling and venting, the contents ofthe bomb were discharged into a reaction flask. The unreacted reactantsand other volatiles were stripped in atmospheric and vacuum pressuresusing a vigreux column. The residue obtained after stripping wastransferred into a 250-ml. flask and fractionated through a 10 platecolumn. The product, which was collected at 150l60 C. and 0.05- 2 mm.Hg. pressure, weighed 52 grams corresponding to 35.2% yield based on theheptafluoropentene charged.

After fractionation of the product on a preparative VPC column, twofractions were obtained.

Elemental analysis, IR and NMR studies showed the following structuresof the two fractions:

(1) 5 (5,5,5,4,4,3,3 heptofluoro-l-pentyl)-2-piperidone.

(2) 3-(5,5,5,4,4,3,3 heptafiuoro 1 pentyl)-2-piperidone.

The two isomeric products are solid at room temperature. The ratio ofisomers (l) and (2) is 1.6:1, respectively.

EXAMPLE 5 Into a one-liter stainless steel shaker bomb, after a nitrogenpurge, a solution of the following reactants was charged:

e-caprolactam=684 grams (6.0 mole) Di-t-butyl per0Xide=l2.0 grams (0.082mole) The bomb was immediately capped and through its gas valve andcharged with 60 grams (0.6 mole) of tetrafluoroethylene and sealed. Thebomb was then heated with shaking and maintained at -135 C. for 14hours. After cooling, it was vented and the contents of the bombdischarged into a one-liter reaction flask and the excess reactantsstripped in vacuum using a 6-inch vigreux column. The residue wastransferred into a 500 ml. flask and fractionated through a 12-inchpacked column. The product was collected at 160 C. at 0.5-4 mm. Hgpressure. It weighed 53 grams, corresponding to 41.3% yield based on thetetrafiuoroethylene used.

After fractionation of the product on a preparative VPC column, twofractions were obtained.

Elemental analysis, IR and NMR studies showed the following structuresof the two fractions:

(1) 7-(1,1,2,2-tetrafluoroethyl)caprolactam.

(2) 3-(1,1,2,2-tetrafiuoroethyl)caprolactam.

The two isomeric products are solids at room temperature. The ratio ofisomers (l) and (2) is 1.5:1, respectively.

EXAMPLE 6 Into a one-liter stainless steel shaker bomb, after a nitrogenpurge, a solution of the following reactants was charged:

N-hydroxyethyl-Z-pyrrolidone=645 grams (5 moles) Di-t-butyl peroxide=15grams (0.1 mole) The bomb was immediately capped through its gas valveand charged with 75 grams (0.5 mole) of hexafluoropropylene and sealed.The bomb was then heated with shaking and maintained at 125-140 C. for12 hours. After cooling, it was vented and the contents of the bombdischarged into a one-liter reaction flask and the excess reactantsflask distilled in vacuum. The residue was transferred to a 250 ml.fiask and flask distilled at a low vacuum of 0.01 to 0.05 mm. Hg at C.-C. The product weighed 19.8 grams, corresponding to 14.1 yield based onthe hexafiuoropropylene.

After fractionation of the product on a preparative VPC column, threefractions were obtained.

Elemental analysis, IR and NMR studies showed the following structuresof the three fractions:

(1) 5-(1,1,2,3,3,3 hexafluoropropyl)N-hydroxyethyl- 2-pyrrolidone.

(2) 3-(1,1,2,3,3,3 hexafiuoropropyl)N-hydroxyethyl- Z-pyrrolidone.

(3) N-(l-hydroxymethyl-2,2,3,4,4,4-hexafiuorobutyl)- 2-pyrrolidone.

The three isomeric products are solids at room temperature. The ratio ofisomers (1), (2) and (3) is 4:3: 1, respectively.

The mono-haloalkylated and poly-haloalkylated lactams, hereinafterreferred to simply for sake of brevity as haloalkylated lactams, asabove prepared, are excellent solvents for polystyrene,polyacrylonitrile, cellulose triacetate, shellac, etc. They areexcellent paint and varnish film softeners and are especially useful inpaint and varnish removal formulations. In view of their polyhalogencontent, they exhibit an extremely low fire hazard. They are especiallyadaptable in petroleum processing; in specialty inks, and in the dyeingof polyacrylonitrile fibers with acetate dyes. They are excellentswelling agents for cellulose acetate films, fibers and as solvents inthe welding of plastic films and in adhesive applications.

The polyhaloalkylated lactams are effective nematocides. They are usefulas intermediates for preparation of agricultural pesticides, dyes andfire-retardant compositions. They are excellent solvents in dye bathsfor dyeing synthetic fibers. They are especially suitable for meltspinning of polyacrylonitrile. Solutions of polymers of acrylonitrile inthe polyhaloalkylated lactams are particularly adaptable for wet or dryspinning into fibers, and for casting into films or sheets.

In the polymerization of pyrrolidone in the presence of an alkalinepolymerization catalyst, the polyhaloalkylated lactams increase the rateof polymerization, the yield, as well as the quality of the resultingpolymer. The polyhaloalkylated lactams are useful as selective solventsfor hydrocarbons, such as, in the separation of liquid aromaticolefinic, naphthenic and paraffinic hydrocarbons from one another bysolvent extraction and extractive distillation. In the thermalpolymerization of caprolactam, they initiate the polymerization in theabsence of any other reactants. They are excellent polymerizationinhibitors of diacetylene compounds. Their addition to hectographtransfer solvents reduces flammability and improves the copy quality.They are useful as shrinking agents for the shrinking and setting ofpolyacrylonitrile textile filaments. They are excellent for solventextraction, especially gas oils for removal of metal contaminants. Thepolyhaloalkylated lactams are more selective than phenol or furfural formetal removal in solvent extraction processes, and are readily recoveredby distillation.

We claim:

1. A lactam having the following formula:

R1 N H wherein R and R are selected from the group consisting ofhydrogen, methyl and ethyl, n is an integer of from 1 to 3, and X is apolyhaloalkyl of from 3 to 6 carbon atoms wherein the polyhalosubstituents in said polyhaloalltyl are at least 2 halo substituents ofthe group consisting of chlorine and fluorine.

2. A lactam having the following formula:

wherein the X's are independently selected from the group consisting ofhydrogen and polyhaloalkyl of from 3 to 6 carbon atoms wherein thepolyhalo substituents in said polyhaloalkyl are at least 2 halosubstituents of the group consisting of chlorine and fluorine, andwherein at least one of the Xs is the said polyhaloalkyl.

3. The process of preparing haloalkylated lactams which comprisesheating in a sealed container from 5 to 20 moles of a lactam having thefollowing formula:

wherein R and R are selected from the group consisting of hydrogen,methyl and ethyl, R is selected from the group consisting of hydrogen,alkyl of from 1 to 18 carbon atoms, aminoalkyl of from 1 to 18 carbonatoms and hydroxyalkyl of from 1 to 18 carbon atoms, and n is an integerof from 1 to 3, with one mole of a halogenated-u-olefin selected fromthe group consisting of monohalo-a-olefin and polyhalo-a-olefin of atleast 2 carbon atoms at a temperature of from to 200 C. in the presenceof from 0.05 to 0.25 mole of an organic peroxide.

4. The process of preparing haloalkylated lactams which comprisesheating in a sealed container from 5 to 20 moles of a lactam having thefollowing formula:

wherein n is an integer of from 1 to 3 with one mole of ahalogenateda-olefin selected from the group consisting ofmonohalo-u-olefin and polyhalo-a-olefin of at least 2 carbon atoms at atemperature of from 80 to 200 C. in the presence of from 0.05 to 0.25mole of an organic peroxide.

5. The process according to claim 3 wherein the lactam is 2-pyrrolidone.

6. The process according to claim 3 wherein the lactam isN-methyl-Z-pyrrolidone.

7. The process according to claim 3 wherein the lactam is 2-piperidone.

8. The process according to claim 3 wherein the lactam is e-caprolactam.

9. The process according to claim 3 wherein the lactam isN-hydroxyethyl-2-pyrrolidone.

References Cited FOREIGN PATENTS 7/1965 Belgium. 7/1965 Belgium.

OTHER REFERENCES HENRY R. IILES, Primary Examiner.

ROBERT T. BOND, Assistant Examiner.

